Guan Zong-Jie, Hu Feng, Yuan Shang-Fu, Nan Zi-Ang, Lin Yu-Mei, Wang Quan-Ming
Department of Chemistry , College of Chemistry and Chemical Engineering , Xiamen University , Xiamen , 361005 , PR China . Email:
Department of Chemistry , Tsinghua University , Beijing , 100084 , PR China.
Chem Sci. 2019 Feb 4;10(11):3360-3365. doi: 10.1039/c8sc03756f. eCollection 2019 Mar 21.
We report the synthesis and structures of two 34-atom metal nanoclusters, namely [Ag(BTCA)(C[triple bond, length as m-dash]CBu )(tfa)(CHOH)]SbF and [AuAg(BTCA)(C[triple bond, length as m-dash]CBu )(tfa)(CHOH)]SbF, where HBTCA is -butylthiacalix[4]arene and tfa is trifluoroacetate. Their compositions and structures have been determined by single-crystal X-ray structural analysis and ESI-MS. The cationic cluster consists of a centered icosahedron M@Ag (M = Ag or Au) core that is surrounded by 21 peripheral silver atoms. Surrounding protection is provided by four kinds of ligands, including three BTCA, nine BuC[triple bond, length as m-dash]C, four tfa, and three methanol solvent ligands. It was found that the Ag@BTCA μ-coordination motif of thiacalixarene is critical for high stability of the title clusters, and extra stability enhancement can be achieved by doping a gold atom at the center of the silver cluster. This work suggests that coordination saturation should be taken into account in addition to electronic and geometric factors for analyzing metal nanocluster stabilities.
我们报道了两种34原子金属纳米簇合物的合成及结构，即[Ag(BTCA)(C≡CBu)(tfa)(CHOH)]SbF和[AuAg(BTCA)(C≡CBu)(tfa)(CHOH)]SbF，其中HBTCA为-丁基硫杂杯[4]芳烃，tfa为三氟乙酸酯。它们的组成和结构已通过单晶X射线结构分析和电喷雾电离质谱法确定。阳离子簇合物由一个中心二十面体M@Ag（M = Ag或Au）核组成，该核被21个外围银原子包围。四种配体提供了周围保护，包括三个BTCA、九个BuC≡C、四个tfa和三个甲醇溶剂配体。发现硫杂杯芳烃的Ag@BTCA μ-配位模式对标题簇合物的高稳定性至关重要，并且通过在银簇中心掺杂一个金原子可以实现额外的稳定性增强。这项工作表明，在分析金属纳米簇稳定性时，除了电子和几何因素外，还应考虑配位饱和度。
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